U.S. patent application number 10/968048 was filed with the patent office on 2005-05-19 for process for preparing fluoropolymer dispersions.
This patent application is currently assigned to Solvay Solexis S.p.A.. Invention is credited to Kapeliouchko, Valeri, Malvasi, Marco.
Application Number | 20050107506 10/968048 |
Document ID | / |
Family ID | 34385819 |
Filed Date | 2005-05-19 |
United States Patent
Application |
20050107506 |
Kind Code |
A1 |
Kapeliouchko, Valeri ; et
al. |
May 19, 2005 |
Process for preparing fluoropolymer dispersions
Abstract
A process for preparing fluoropolymer dispersions, substantially
free from anionic fluorinated surfactants, and with a coagulum
amount <0.1% by weight, comprising: a) step a1) addition of: a
non ionic surfactant having cloud point (CP) between 40.degree. and
80.degree. C., in an amount from 1.5% to 50% by weight on the
dispersion fluoropolymer; and optionally an electrolyte to bring
the specific conductivity of the dispersion to values in the range
130-8,000 .mu.S/cm; optionally a buffer agent to have a pH between
2 and 12 to a fluoropolymer dispersion obtainable by an emulsion
polymerization process; step a2): heating of the dispersion
obtained in a1) up to a temperature T.sub.c in the range
CP.+-.10.degree. C.; decantation without stirring, at the
temperature T.sub.c, until obtaining the dispersion separation in
two aqueous phases, of which the lower one containing the
fluoropolymer is discharged; b) step b1): the dispersion obtained
in step a2) is optionally additioned of an electrolyte and of a non
ionic surfactant as in a1).
Inventors: |
Kapeliouchko, Valeri;
(Alessandria, IT) ; Malvasi, Marco; (Alessandria,
IT) |
Correspondence
Address: |
ARENT FOX KINTNER PLOTKIN & KAHN
1050 CONNECTICUT AVENUE, N.W.
SUITE 400
WASHINGTON
DC
20036
US
|
Assignee: |
Solvay Solexis S.p.A.
|
Family ID: |
34385819 |
Appl. No.: |
10/968048 |
Filed: |
October 20, 2004 |
Current U.S.
Class: |
524/379 ;
524/423; 524/544 |
Current CPC
Class: |
C08F 6/16 20130101; C08J
3/03 20130101; C08F 6/16 20130101; C08J 2327/12 20130101; C08F 6/20
20130101; C08L 27/12 20130101; C08L 27/12 20130101; C08F 6/20
20130101 |
Class at
Publication: |
524/379 ;
524/423; 524/544 |
International
Class: |
C08L 001/00 |
Foreign Application Data
Date |
Code |
Application Number |
Oct 21, 2003 |
IT |
MI2003 A 002050 |
Claims
1. A process for the preparation of pumpable fluoropolymer
dispersions, preferably based on tetrafluoroetilene (TFE)
homopolymers or copolymers, substantially free from anionic
fluorinated surfactants, and with a coagulum amount <0.1% by
weight, preferably <0.01% by weight, still more preferably
<0.005% by weight referred to the polymer weight, comprising: a)
step a1) addition of: a nonionic surfactant having cloud point (CP)
between 40.degree. and 80.degree. C., in an amount from 1.5% to 50%
by weight, preferably from 2.5% to 30% by weight on the dispersion
fluoropolymer; and optionally an electrolyte in an amount such to
bring the specific conductivity of the dispersion, measured at
25.degree. C., to values in the range 130-8,000 .mu.S/cm,
preferably 250-3,000 .mu.S/cm; and optionally a buffer agent to
have a pH between 2 and 12, preferably between 3 and 10, to a
fluoropolymer dispersion obtainable by an emulsion polymerization
process; Step a2): heating of the dispersion obtained in step a1),
under stirring, up to a temperature T.sub.c in the range
CP.+-.10.degree. C., preferably in the range CP.+-.5.degree. C., CP
being the cloud point of the used nonionic surfactant; decantation
without stirring, by operating at the temperature T.sub.c, until
obtaining the dispersion separation in the following aqueous
phases: a lower phase wherein the concentrated fluoropolymer is in
the range 40%-75% w/w, preferably 60%-75% w/w, a surnatant phase
substantially not containing fluoropolymer; surnatant separation;
discharge of the lower phase containing the concentrated
fluoropolymer; b) Step b1): the discharged dispersion obtained in
step a2), after surnatant separation, is additioned: optionally, of
an electrolyte in an amount such to bring the specific conductivity
of the dispersion, measured at 25.degree. C., to values in the
range 130-8,000 .mu.S/cm, preferably 250-3,000 .mu.S/cm; a nonionic
surfactant having cloud point (CP) in the range
40.degree.-80.degree. C., and such to be present in the dispersion
in an amount from 1.5% to 50% by weight, preferably from 2.5% to
30% by weight on the dispersion fluoropolymer; optionally, a buffer
agent to have a pH in the range 2-12, preferably 3-10; Step b2):
repetition of the steps indicated in step a2); optionally c) Step
c1): repetition of step b1) but using the dispersion obtained in
step b2); step c2): repetition of the steps indicated in step
b2).
2. A process according to claim 1, wherein the fluoropolymer
dispersions obtainable with an emulsion or microemulsion
polymerization process, have the following characteristics:
particle diameter from 10 nm to 400 nm, preferably from 20 nm to
300 nm, fluoropolymer concentration from 10% to 45% by weight,
preferably from 20% to 35%, amount of fluorinated anionic
surfactant in the range 800 ppm-10,000 ppm, preferably 1,200
ppm-6,000 ppm referred to the polymer weight.
3. A process according to claim 1, wherein the fluoropolymer
dispersions obtainable by an emulsion or microemulsion
polymerization process are polytetrafluoroethylene (PTFE)
dispersions wherein the amount of fluorinated anionic surfactant is
in the range 2,500 ppm-5,000 ppm, preferably 3,000 ppm-4,000 ppm
referred to the polymer weight.
4. A process according to claim 1, wherein when the surfactant
amount in the initial dispersion, obtainable with an emulsion or
microemulsion polymerization process, is lower than about 3,000 ppm
referred to the fluoropolymer weight, and the fluoropolymer
concentration in the dispersion is about 30% by weight, steps a)
and b) are carried out to obtain fluoropolymer dispersions
substantially anionic fluorinated surfactant free.
5. A process according to claim 1, wherein when the surfactant
amount in the initial dispersion is higher than 3,000 ppm referred
to the fluoropolymer weight and operating with a fluoropolymer
concentration in the dispersion of about 30% by weight, three steps
a), b) and c) are necessary.
6. A process according to claim 1, wherein the dispersions
substantially anionic fluorinated surfactant free contain a
surfactant amount lower than 100 ppm referred to the polymer
weight.
7. A process according to claim 1, comprising, in addition to steps
a)-c), also the following one: d) Step d1): repetition of step c1)
but by using the dispersion obtained in step c2); Step d2):
repetition of the steps indicated in step c2).
8. A process according to claim 7, comprising, in addition to steps
a), b), c), d) also step e) and optionally step f): e) Step e1):
repetition of step d1) but by using the dispersion obtained in step
d2); Step e2): repetition of the steps indicated in step d2); f)
Step f1): repetition of step e1) but by using the dispersion
obtained in step e2); Step f2): repetition of the steps indicated
in step e2).
9. A process according to claim 1, wherein in steps a2), b2), c2),
d2), e2), f2) the supernatant is purified to recover the
surfactants, in particular the anionic fluorinated surfactants by
treatment with solid adsorbers, preferably anionic exchange
resins.
10. A process according to claim 1, wherein in steps a1), b1), c1),
d1), e1), f1) one or more surfactants are used, the mixture of
which has a CP value in the range indicated in a1).
11. A process according to claim 1, wherein the nonionic
surfactants have a CP from 45.degree. C. to 70.degree. C.
12. A process according to claim 11, wherein the nonionic
surfactants are selected from polyethoxylated alcohols and
polyethoxylated alkylphenols which can contain one or more
propylene oxide units.
13. A process according to claim 11, wherein the nonionic
surfactants are selected from the following ones:
t-C.sub.8H.sub.17--C.sub.6H.sub.4--(OCH- .sub.2CH.sub.2).sub.9-10
OH sec-C.sub.12H.sub.25--(OCH.sub.2CH.sub.2).sub.- 10,1OH
iso-C.sub.13H.sub.27--(OCH.sub.2CH.sub.2CH.sub.2)--(OCH.sub.2CH.sub-
.2).sub.10--OH iSo-C.sub.13H.sub.27--(OCH.sub.2CH.sub.2).sub.10--OH
iSo-C.sub.13H.sub.27--(OCH.sub.2CH.sub.2).sub.8--OH.
14. A process according to claim 1, wherein the electrolytes used
are ammonium salts or hydroxides and/or alkaline metals, preferably
selected from ammonium sulphate, ammonium bisulphate, ammonium
carbonate, ammonium hydroxide.
15. A process according to claim 1, wherein the fluoropolymers of
the dispersions obtainable by emulsion or microemulsion
polymerization are the TFE copolymers or PTFE homopolymers.
Description
[0001] The present invention relates to a process for preparing
aqueous dispersions of fluoropolymers substantially free from
fluorinated surfactants, in particular fluorinated ionic
surfactants.
[0002] More specifically the present invention relates to a process
for preparing aqueous dispersions of fluoropolymers substantially
free from perfluorooctanoate in the form of acid or its salts.
[0003] With aqueous dispersions of fluoropolyemrs substantially
free from fluorinated surfactants it is meant that the content of
fluorinated surfactants referred to the fluoropolymer weight is
lower than 100 ppm, in particular lower than 50 ppm, more
specifically lower than 5 ppm.
[0004] It is well known in the prior art that for the production of
fluorinated polymers there are two different polymerization
methods: the suspension polymerization and the emulsion
polymerization.
[0005] In the suspension polymerization polymer granules having
millimetric sizes are obtained.
[0006] In the emulsion polymerization a colloidal aqueous
dispersion is obtained having particle sizes from some nanometres,
generally 10 nm, to hundreds nanometres, from 100 nm to 400 nm. The
emulsion polymerization process of fluoropolymers is carried out
with a slow stirring and in the presence of surfactants not acting
as chain transfer agent to avoid to obtain fluoropolymers having a
low molecular weight and therefore having poor mechanical
properties. Said surfactants are called non telogenic surfactants,
see, for example, U.S. Pat. No. 2,559,752. Perfluoroalkanoic acid
salts, in particular, the ammonium salt and/or alkaline metal salts
of the perfluorooctanoic acid, hereinafter indicated as PFOA, are
industrially very often used. Other (per)fluorinated anionic
surfactants are also used, see for example U.S. Pat. No. 3,271,341,
U.S. Pat. No. 4,380,618, U.S. Pat. No. 4,864.006, U.S. Pat. No.
5,789,508.
[0007] The PFOA is the most industrially used surfactant in the
emulsion polymerization since it is not telogen, thus allowing to
obtain fluorinated polymer dispersions having high molecular
weight, and it allows to obtain stable dispersions for long periods
of time.
[0008] It is also known that in the applications of fluoropolymer
dispersions, as coating or in the impregnation of glass fibers,
said fluorinated surfactants can reach the environment, for example
by the washing effluents, or because they disperse in the
atmosphere during the drying and/or sintering steps. However some
of said surfactants have been classified as harmful for the
environment and are characterized by a low bioelimination rate from
the human body. For example, the PFOA seems to belong to the
surfactants particularly harmful for the environment and with long
residence time in men. Therefore there is a request from the users
of fluoropolymer dispersions substantially free from fluorinated
anionic surfactants, and in particular free from PFOA.
[0009] The fluoropolymer dispersions are obtained from the emulsion
polymerization process with a fluorinated polymer concentration in
the range 20-35% by weight referred to 100 parts by weight of the
dispersion.
[0010] The fluoropolymer dispersions obtained from the
polymerization process can be subjected to post-treatments to
obtain concentrated fluoropolymer dispersions, even up to 75% w/w.
The concentration processes can be obtained, for example, by a
decantation process as described, for example, in U.S. Pat. No.
3,037,953, U.S. Pat. No. 3,704,272 and U.S. Pat. No. 3,301,807. In
these patents no reference is made to the PFOA reduction in the
obtained fluoropolymer dispersions.
[0011] Another concentration process of fluoropolymer dispersions
is the so called ultrafiltration process as described, for example,
in U.S. Pat. No. 6,136,893 and U.S. Pat. No. 4,369,266. In U.S.
Pat. No. 4,369,266 it is described also a variant of the
ultrafiltration process, allowing to obtain aqueous dispersions of
fluoropolymers substantially free from fluorinated anionic
surfactant, for example PFOA. The process is based on the
fluoropolymer dispersions dialysis and the permeate is purified
from PFOA by using anionic exchange resins. This process can be
industrially carried out. The drawback of this process is due to
the fact that the dialysis process is slow, in particular to obtain
fluoropolymer dispersions having a very low PFOA content, lower
than 10 ppm referred to the polymer weight.
[0012] It is also known a process for obtaining polymeric
dispersions substantially free from PFOA by direct contact of the
stabilized dispersion with anionic exchange resins. See for example
U.S. Pat. No. 3,536,643, EP 1,155,055, WO 03/051988. This process
allows to obtain dispersions substantially free from PFOA with a
good productivity, however it has the drawback that a part of
fluoropolymer particles can remain in the anionic exchange resins
when this process is industrially carried out. This drawback can
happen if the stabilized fluoropolymer dispersion results locally
unstabilized, for any reason, and therefore with coagulum
formation. Or because a physical fluoropolymer trapping takes
place. This involves a fluoropolymer loss, and above all it
prevents the resin regeneration process with the drawback of the
exhausted resins disposal.
[0013] In patent application DE 100 18 853 it is described a
process for obtaining dispersions substantially free from PFOA by
distillation of the dispersion brought to pH between 1 and 3. Said
process has the drawback to involve a strong dispersion
destabilization and a high probability of coagulum formation.
Besides, there is the drawback of the formation of a remarkable
amount of foam creating problems in an industrial process.
[0014] The need was felt of a process to obtain fluoropolymer
dispersions, capable to overcome the inconveniences of the above
described processes of the prior art, having the following
characteristics:
[0015] substantially fluorinated surfactant free, in particular
fluorinated anionic surfactants;
[0016] pumpability, in industrial plant pipes by using non critical
pressure values for the stability of the dispersion itself;
[0017] containing a coagulum amount <0.1% by weight, preferably
<0.01% by weight referred to the polymer weight.
[0018] It has been found by the Applicant a process allowing to
solve the above technical problem.
[0019] An object of the present invention is a process for the
preparation of pumpable fluoropolymer dispersions, preferably based
on tetrafluoroethylene (TFE) homopolymers or copolymers,
substantially free from anionic fluorinated surfactants, and with a
coagulum amount <0.1% by weight, preferably <0.01%, still
more preferably <0.005% by weight referred to the polymer
weight, comprising:
[0020] a)
[0021] Step a1) addition of:
[0022] a non ionic surfactant having cloud point (CP) between
40.degree. and 80.degree. C., in an amount from 1.5% to 50% by
weight, preferably from 2.5% to 30% by weight on the dispersion
fluoropolymer; and
[0023] optionally an electrolyte in an amount such to bring the
specific conductivity of the dispersion, measured at 25.degree. C.,
to values in the range 130-8,000 .mu.S/cm, preferably 250-3,000
.mu.S/cm; and
[0024] optionally a buffer agent to have a pH between 2 and 12,
preferably between 3 and 10,
[0025] to a fluoropolymer dispersion obtainable by an emulsion or
microemulsion polymerization process;
[0026] Step a2):
[0027] heating of the dispersion obtained in step a1), under
stirring, up to a temperature T.sub.c in the range CP.+-.10.degree.
C., preferably in the range CP.+-.5.degree. C., CP being the cloud
point of the used nonionic surfactant;
[0028] decantation without stirring, by operating at the
temperature T.sub.c, until obtaining the dispersion separation in
the following aqueous phases:
[0029] a lower phase containing the concentrated fluoropolymer,
wherein the fluoropolymer concentration is in the range 40%-75%
w/w, preferably 60%-75% w/w,
[0030] a surnatant phase substantially not containing
fluoropolymer;
[0031] surnatant separation;
[0032] discharge and recovery of the lower phase containing the
concentrated fluoropolymer;
[0033] b)
[0034] step b1):
[0035] the dispersion of the recovered lower phase obtained in step
a2), after surnatant separation, is additioned:
[0036] optionally, with an electrolyte in an amount such to bring
the specific conductivity of the dispersion, measured at 25.degree.
C., to values in the range 130-8,000 .mu.S/cm, preferably 250-3,000
.mu.S/cm;
[0037] a non ionic surfactant having cloud point (CP) in the range
40.degree.-80.degree. C., and such to be present in the dispersion
in an amount from 1.5% to 50% by weight, preferably from 2.5% to
30% by weight on the dispersion fluoropolymer;
[0038] optionally, a buffer agent to have a pH in the range 2-12,
preferably 3-10;
[0039] Step b2):
[0040] repetition of the steps indicated in step a2);
optionally
[0041] c)
[0042] Step c1):
[0043] repetition of step b1) but by using the dispersion obtained
in
[0044] Step b2);
[0045] Step c2):
[0046] repetition of the steps indicated in step b2).
[0047] The fluoropolymer dispersions obtainable with an emulsion or
microemulsion polymerization process, generally have the following
properties:
[0048] particle diameter from 10 nm to 400 nm, preferably from 20
nm to 300 nm,
[0049] fluoropolymer concentration from 10% to 45% by weight,
preferably from 20% to 35%,
[0050] amount of fluorinated anionic surfactant in the range 800
ppm-10,000 ppm, preferably 1,200 ppm-6,000 ppm referred to the
polymer weight.
[0051] From the industrial point of view polytetrafluoroethylene
(PTFE) dispersions obtainable by an emulsion polymerization process
typically have an amount of fluorinated anionic surfactant in the
range about 2,500 ppm-about 5,000 ppm, preferably 3,000 ppm-4,000
ppm referred to the polymer weight.
[0052] It has been found by the Applicant that when the surfactant
amount in the initial fluoropolymer dispersion, obtainable with an
emulsion or microemulsion polymerization process, is lower than
about 3,000 ppm referred to the fluoropolymer weight, and for
fluoropolymer concentrations in the dispersion of about 30% by
weight, steps a) and b) are sufficient to obtain fluoropolymer
dispersions substantially anionic fluorinated surfactant free. When
the surfactant amount in the initial dispersion is higher than
about 3,000 ppm referred to the fluoropolymer weight and operating
with a fluoropolymer concentration of about 30' by weight, three
steps (a)+b)+c)) are necessary.
[0053] With pumpable fluoropolymer dispersions, according to the
present invention, dispersions are meant running or flowing in
industrial plant pipes by using non critical pressure values for
the dispersion stability. Generally these pressure values range
from 1.5 to 10 bar.
[0054] It has been surprisingly and unexpectedly found that with
the above process, the fluoropolymer dispersions are substantially
anionic fluorinated surfactant free: the amount of said surfactant
is lower than 100 ppm referred to the polymer weight. This allows
to accomplish an industrial plant.
[0055] Preferably the above described invention process comprises
besides steps a), b), c), also the following step:
[0056] d)
[0057] Step d1):
[0058] repetition of step c1) but by using the dispersion obtained
in
[0059] Step c2);
[0060] Step d2):
[0061] repetition of the steps indicated in step c2).
[0062] The fluoropolymer dispersions obtained in step d2) contain
an even lower amount of said anionic fluorinated surfactant.
[0063] Still more preferably the above invention process comprises,
besides steps a), b), c), d) also step e) and optionally the
successive step f), to obtain fluoropolymer dispersions containing
a few ppm of fluorinated anionic surfactant:
[0064] e)
[0065] Step e1):
[0066] repetition of step d1) but by using the dispersion obtained
in
[0067] Step d2);
[0068] Step e2):
[0069] repetition of the steps indicated in step d2)
[0070] f)
[0071] Step f1):
[0072] repetition of step e1) but by using the dispersion obtained
in
[0073] Step e2);
[0074] Step f2):
[0075] repetition of the steps indicated in step e2).
[0076] In step a2) the surnatant is purified to recover the
surfactants, in particular the anionic fluorinated surfactants.
This is carried out by treatment with solid adsorbers, preferably
anionic exchange resins. All the other surnatants obtained in steps
b2), c2), d2), e2), f2) can be subjected to the above process to
recover the surfactants.
[0077] In steps a1), b1), c1), d1), e1), f1) one or more
surfactants can be used so that the surfactant mixture has a CP
value in the range indicated in a1). The mixture CP is measured
according to the methods mentioned in the Examples.
[0078] The nonionic surfactants used in the process of the present
invention having cloud point (CP) in the range 400.degree.
C.-80.degree. C. are known in the prior art. The book "Nonionic
surfactants" Ed. M. J. Schick, Marcel Dekker 1967, pages 76-85 and
103-141 can for example be mentioned. Preferably the nonionic
surfactants used in the process of the present invention have a CP
from 45.degree. C. to 700.degree. C. Among nonionic surfactants,
polyethoxyated alcohols and polyethoxylated alkylphenols are
particularly preferred, optionally containing one or more propylene
oxide units. The following surfactants are those still more
preferred:
[0079] Triton.RTM.X100 (Dow), having formula:
t-C.sub.8H.sub.17--C.sub.6H.sub.4--
(OCH.sub.2CH.sub.2).sub.9-10OH
[0080] Tergitol.RTM.TMN100x (Dow), having formula:
sec-C.sub.12H.sub.25-- (OCH.sub.2CH.sub.2).sub.10,1OH
[0081] Antarox.RTM.863 (Rhodia), having formula:
iSo-C.sub.13H.sub.27-- (OCH.sub.2CH.sub.2CH.sub.2)--
(OCH.sub.2CH.sub.2).sub.10--OH
[0082] Rhodasurf.RTM.870 (Rhodia), having formula:
iso-C.sub.13H.sub.27-- (OCH.sub.2CH.sub.2).sub.10--OH
[0083] Genapol.RTM.X080 (Clariant), having formula:
iso-C.sub.13H.sub.27-- (OCH.sub.2CH.sub.2).sub.8--OH.
[0084] In the process of the present invention mixtures of nonionic
surfactants can be used, provided that the mixture cloud point is
within the above limits.
[0085] The preferred electrolytes used in the present invention are
ammonium salts or hydroxides and/or alkaline metals. The following
are still more preferred: ammonium sulphate, ammonium bisulphate,
ammonium carbonate, ammonium hydroxide.
[0086] The process of the present invention can be used for the
purification of fluorinated anionic surfactants also for
fluoropolymer dispersions containing more than 10,000 ppm of said
surfactants, referred to the polymer weight. In this case the
process of the present invention comprises a greater number of
phase separation steps.
[0087] Among the anionic exchange resins usable in the process of
the present invention to purify the supernatant from fluorinated
anionic surfactants, there can be mentioned the anionic exchange
resins described in "Kirk-Othmer--Encyclopedia of Chemical
Technology" vol. 14, pages 737-783, J. Wiley & Sons, 1995.
Among the preferred anionic exchange resins there can be mentioned
the resins containing a tertiary or quaternary ammonium group.
Among the preferred commercial resins, Amberje.RTM.4400 OH
(Rohm&Haas) and Dowex.RTM.MSA 1-C (Dow) can be mentioned.
[0088] As other usable solid adsorbers, one can mention active
carbons, alumina, silicas, inorganic hydroxides having low
solubility in water, for example magnesium and calcium
hydroxide.
[0089] Among the buffer agents usable in the process of the present
invention, there can be mentioned the well known organic or
inorganic buffer systems of the prior art as those formed of a weak
acid in the presence of one of its salts with a strong base, as
CH.sub.3COOH/CH.sub.3COONa, NaHCO.sub.3/Na.sub.2CO.sub.3, or those
formed of a weak base in the presence of one of its salts with a
strong acid, for example NH.sub.4OH/NH.sub.4Cl.
[0090] The polymerization processes to obtain the dispersions
usable in the process of the present invention are the emulsion or
microemulsion polymerization processes.
[0091] The emulsion polymerization processes are described in the
following patents: U.S. Pat. No. 2,559,752, U.S. Pat. No.
4,380,618, U.S. Pat. No. 5,789,508, U.S. Pat. No. 6,479,591, U.S.
Pat. No. 6,576,703 and in the patent application U.S.
2003/0153674.
[0092] The microemulsion polymerization processes are described in
the following patents in the name of the Applicant: U.S. Pat. No.
4,864,006 and U.S. Pat. No. 6,297,334.
[0093] The microemulsions usable in the microemulsion
polymerization processes are described in U.S. Pat. No. 4,864,006
and U.S. Pat. No. 4,990,283.
[0094] The dispersion fluoropolymers used in the process of the
present invention are for example:
[0095] tetrafluoroethylene (TFE) homopolymers and TFE copolymers
with monomers having at least one unsaturation of ethylene
type;
[0096] thermoprocessable fluoropolymers (from the melt) based on
TFE as PFA, MFA, FEP and ETFE;
[0097] VDF-based homopolymers and copolymers;
[0098] CTFE-based homopolymers and copolymers, for example PCTFE
and E/CTFE copolymer;
[0099] VDF-based fluoroelastomers;
[0100] VDF/HFP, optionally containing TFE and/or vinylethers
selected from perfluoroalkylvinylethers and/or
perfluoroalkoxyalkylvinylethers; optionally containing hydrogenated
olefins as ethylene and propylene;
[0101] TFE-based (per)fluoroelastomers:
[0102] TFE copolymers with vinylethers selected from
perfluoroalkylvinylethers and/or perfluoroalkoxyalkylvinylethers;
in particular TFE/PMVE, TFE/PEVE, TFE/PPVE;
[0103] TFE copolymers with hydrogenated olefins, preferably
ethylene and/or propylene;
[0104] TFE and/or VDF amorphous and/or crystalline fluoropolymers
containing dioxole rings having 5-7 atoms, in particular those
obtained by copolymerization with (per)fluorodioxcles or with
dienic monomers giving dioxole rings by cyclization.
[0105] The copolymers of tetrafluoroethylene (TFE) with monomers
having at least one unsaturation of ethylene type comprise
comonomers of hydrogenated and fluorinated type. The comonomer
amount is preferably lower than 3% by weight, preferably lower than
1% to have non thermoprocessable copolymers (the so called modified
PTFE).
[0106] Among the hydrogenated comonomers it can be mentioned
ethylene, propylene, acrylic monomers, for example
methylmethacrylate, (meth) acrylic acid, hydroxyethylenacrylate,
styrene monomers, as, for example, styrene.
[0107] Among the fluorinated comonomers there can be mentioned:
[0108] C.sub.3-C.sub.8 perfluoroolefins, as hexafluoropropene
(HFP)
[0109] C.sub.2-C.sub.8 hydrogenated fluoroolefins, such as vinyl
fluoride (VF), vinylidene fluoride (VDF), trifluoroethylene,
[0110] CH.sub.2.dbd.CH--R.sub.f0 perfluoroalkylethylene, wherein
R.sub.f0 is a C.sub.1-C.sub.6 perfluoroalkyl;
[0111] C.sub.2-C.sub.6 chloro- and/or bromo- and/or
iodo-fluoroolefins, as chlorotrifluoroethylene (CTFE);
[0112] CF.sub.2.dbd.CFOR.sub.f0 (per) fluoroalkylvinylethers
(PAVE), wherein R.sub.f0 is a C.sub.1-C.sub.6 (per)fluoroalkyl, for
example CF.sub.3, C.sub.2F.sub.5, C.sub.3F.sub.7;
[0113] CF.sub.2.dbd.CFOX.sub.0 (per)fluoro-oxyalkylvinylethers,
wherein X.sub.0 is a C.sub.1-C.sub.12 alkyl, or a C.sub.l-C.sub.12
oxyalkyl, or a C.sub.1-C.sub.12 (per)-fluorooxyalkyl having one or
more ether groups, for example perfluoro-2-propoxy-propyl;
[0114] fluorodioxoles, preferably perfluorodioxoles.
[0115] The preferred fluoropolymers of the dispersions obtainable
by emulsion or microemulsion polymerization, usable in the process
of the present invention, are the TFE copolymers or the PTFE
homopolymers.
[0116] The initial dispersion can be mono- bi- or multimodal. For
the bi- and multimodal dispersions see for examples U.S. Pat. No.
6,576,703, U.S. Pat. No. 6,518,352 in the name of the
Applicant.
[0117] The process of the present invention is characterized by a
high efficiency and substantially without fluoropolymer losses.
[0118] The fluoropolymer dispersions essentially free from
fluorinated anionic surfactants obtained with the process of the
present invention are characterized by a good stability to shear
and can be used in the usual applications foreseen for this kind of
compositions. The dispersions obtained with the invention process,
as such or formulated, can also be used for the coating of surfaces
of organic and/or inorganic polymers, of metals or ceramics; for
the glass fiber impregnation, the cast film production, for the
additivation of polymers or inorganic materials etc.
[0119] Without being bound to any theory, researches carried out by
the Applicant have shown that the concentration process by
decantation takes place through a reversible flocculation
mechanism. It is well known that the flocculation reversibility
strongly depends on the presence of a fluorinated anionic
surfactant generating an electrostatic repulsion potential among
the fluoropolymer particles. The skilled in the art would have
expected a partial or complete irreversibility of the invention
process with consequent coagulum formation as the fluorinated
anionic surfactant is reduced in the dispersion. It has been
surprisingly and unexpectedly found by the Applicant that with the
process of the present invention, concentrated dispersions of
fluoropolymers can be prepared substantially free from fluorinated
anionic surfactants without formation of significant amounts of
coagula <0.1% by weight, preferably <0.01% by weight, still
more preferably <0.005% by weight, referred to the
fluoropolymer. Besides, the dispersions obtainable with the process
of the present invention result pumpable, whereby the industrial
use of the invention process does not show any inconvenience.
[0120] The following Examples illustrate with non limitative
purposes the present invention.
EXAMPLES
[0121] The percentages reported in the Examples are percentages by
weight
[0122] Determination of the Average Particle Diameter in the
Latex
[0123] The average particle diameter is determined by an instrument
based on laser light diffusion, in particular on Photon Correlation
Spectroscopy, equipped with Brookhaven correlator model 2030 AT and
Argon Laser light source having a wave length of 514.5 nm by
Spectra-Physics. The latex samples to be measured are diluted with
water filtered at 0.2 .mu.m on Millipore filter. The scattering
measurement is carried out at room temperature (20.degree. C.) at
an angle of 90.degree.. The latex particle diameter is obtained by
the cumulant method.
[0124] Determination of the Dry Product Content (Polymer) in the
Polymerization Latex
[0125] 20 grams of latex are weighed in a glass beaker and placed
in a stove to dry for 1 hour at 1500.degree. C. The latex dry
content is obtained from the formula:
Dry product %=weight after drying/latex initial weight*100.
[0126] Determination of the Polymer and of the Nonionic Surfactant
Content in the Concentrated Dispersions
[0127] About 1 gram of concentrated dispersion is weighed in an
aluminum shuttle and dried in a stove for 1 hour at 1050.degree. C.
The shuttle is weighed and introduced in a muffle at the
temperature of 400.degree. C. for 10 minutes (sintering). At the
end the shuttle is weighed again.
[0128] The polymer content of the concentrated dispersion is
obtained from the formula: 1 Polymer% = weightaftersintering
initialdispersionweight 100
[0129] The nonionic surfactant content of the concentrated
dispersion is obtained from the formula: 2 surfactant% =
weightafterdrying - weightaftersintering initialdispersionweight
100
[0130] PFOA Determination
[0131] The quantitative determination of the PFOA content in the
dispersion is carried out by the method described in "Encyclopedia
of Industrial Chemistry Analysis", vol. 1, pages 339-340,
Interscience Publishers, New York, N.Y., 1971, and in EP-A
194,690.
[0132] PFOA is converted into methyl ester and the ester content
gaschromatografically analyzed. The method sensitivity limit is of
1 ppm.
[0133] Determination of the Cloud Point (CP) of a Nonionic
Surfactant
[0134] The CP is determined according to the standard EN 1890
Method A, at concentration 1% w/w in water of the nonionic
surfactant.
[0135] Determination of the Stability to Shear
[0136] 300 ml of dispersion are placed in a Waring model laboratory
blender having 1 litre volume beaker. The dispersion is subjected
to strong stirring at 20,000 rpm. The time necessary to determine
the dispersion coagulation under said conditions is determined.
[0137] Determination of the Specific Conductivity
[0138] The specific conductivity is determined at the temperature
of 250.degree. C., by Crison 525 conductimeter.
[0139] Determination of the Coagulum Amount Present in the
Dispersion, Calculated with Respect to the Polymer
[0140] 500 g of dispersion are filtered through a nylon net of
known weight with mesh equal to 50 .mu./m. At the end of the
filtration 500 ml of water are let pass through the net to remove
the dispersion in excess. The net with the possible residue is
dried in a stove at 105.degree. C. for 1 hour and then weighed. The
coagulum amount is determined by the difference with respect to the
initial weight of the net. By dividing the difference by the
polymer amount contained in 500 g of dispersion and multiplying by
100, the coagulum percentage in the polymer is obtained.
[0141] The method sensititivy limit is 0.005% by weight on the
polymer.
Example 1-a
[0142] Polymerization
[0143] 11 grams of the aqueous solution of ammonium
perfluorooctanoate at a concentration 100 g/litre and 31 litres of
carefully degassed demineralized water are fed into a 50 litre
autoclave equipped with a mechanical stirrer and previously put
under vacuum. 140 grams of paraffin with softening point in the
range 52.degree. C.-54.degree. C. were also previously introduced
in the reactor. The autoclave is kept under mechanical stirring and
is pressurized with TFE up to a pressure of 20 bar at a temperature
of 680.degree. C. At this point 500 ml of a solution of
(NH4).sub.2S.sub.2O.sub.8 (APS) and disuccinic peroxide (DSAP)
corresponding to 400 mg of APS and 2000 mg of DSAP are fed into the
autoclave.
[0144] When the pressure in the reactor has decreased of 0.5 bar,
one starts to feed TFE by a compressor so to maintain a constant
pressure of 20 bar inside the reactor. In the meantime the internal
reactor temperature is increased up to 78.degree. C. at a speed of
0.5.degree. C./min. During the reaction 50.6 grams of the aqueous
solution at 100 g/litre of ammonium perfluorooctanoate are fed into
the autoclave. After 90 minutes, the TFE feeding is interrupted,
when 15,800 grams of TFE have reacted, the reactor evacuated and
cooled. The discharged latex has a solid content equal to 30%
w/w.
[0145] The diameter of the primary polymer particles determined by
Laser Light Scattering (LLS) is equal to 248 nm. The PFCA content
is 3,900 ppm with respect to the polymer.
Example 1-B
[0146] Purification and Concentration of the Latex Using as
Surfactant Triton.RTM. X100
[0147] Step a)
[0148] In a 3 litre thermostatable reactor 1800 g of PTFE
dispersion of the Example 1-a are introduced, having a solid
content equal to 30% and a PFOA content equal to 3,900 ppm with
respect to the polymer. As nonionic surfactant, Triton.RTM. X100
having CP=67.degree. C. is used. 360 g of this surfactant at 25% by
weight (16.7% by weight with respect to the polymer) and 9 g of
ammonium sulphate solution at 10% by weight (0.-17% with respect to
the polymer) are added to the dispersion. The mixture, homogeneous,
has a specific conductivity at 25.degree. C. equal to 1280 .mu.S/cm
and pH equal to 4.5. The mixture is heated to 68.degree. C. under
stirring. When this temperature is reached, the stirring is stopped
and the mixture let decant for one hour at the same temperature. It
is observed separation of a concentrated phase in polymer in the
lower part of the reactor and of an upper phase rich in surfactant
Triton.RTM. X100, substantially not containing PTFE.
[0149] At the end the mixture is let cool at room temperature and
from the lower part of the reactor a concentrated dispersion is
discharged, being free from coagula (<0.005% by weight on the
polymer), having a polymer content of 69% by weight and a
Triton.RTM. X100 content equal to 2% by weight. The PFOA content
referred to the polymer is equal to 620 ppm. The upper phase
present in the reactor, rich in surfactant Triton.RTM. X100, is
treated with anionic exchange resins Amberjet.RTM.4400OH (Rohm
& Haas) for the PFOA removal and reused in the process.
[0150] Step b)
[0151] 750 g of the so obtained dispersion are introduced into a 3
litre thermostatable reactor. 240 g of Triton.RTM. X100 at 25% by
weight, 750 g of demineralized water and 4.5 g of ammonium sulphate
solution at 10% are added to the dispersion. The ammonium sulphate
solution amount added in this step is lower than that of the
previous step since the treated latex contains a residual amount of
ammonium sulphate.
[0152] The total content in Triton.RTM. X100 is equal to 14.5% with
respect to the polymer, while the specific conductivity of the
mixture is equal to 1010 .mu.S/cm, the pH equal to 8.3. The
homogeneous mixture is heated to 67.50.degree. C. under
stirring.
[0153] At this point the same process described in the previous
step is repeated finally recovering a concentrated dispersion,
being free from coagula, having a polymer content equal to 71.5%, a
Triton.RTM. X100 content equal to 2% and a PFOA content referred to
the polymer equal to 150 ppm. The upper phase present in the
reactor, rich in surfactant Triton.RTM. X100, is treated as
mentioned above to be reused in the process.
[0154] Step c)
[0155] 710 g of the so obtained dispersion are introduced in a 3 l
thermostatable reactor. 280 g of Triton.RTM. X100 at 25%, 1,000 g
of demineralized water and 4.5 g of ammonium sulphate solution at
10% are added to the dispersion. The total content in Triton.RTM.
X100 is equal to 16.6% with respect to the polymer, while the
specific conductivity of the mixture, appearing homogeneous, is
equal to 950 .mu.S/cm, the pH equal to 8.4. The mixture is heated
to 67.5.degree. C. under stirring.
[0156] At this point the same process described in the previous
step is repeated finally recovering a concentrated dispersion,
resulting coagula free, having a polymer content equal to 67% and a
Triton.RTM. X100 content equal to 2.1%. The PFOA content referred
to the polymer is equal to 42 ppm. The upper phase present in the
reactor, rich in surfactant Triton.RTM. X100, is treated as
mentioned above to be reused in the process.
[0157] Step d)
[0158] 740 g of the so obtained dispersion are introduced in a 3 l
thermostatable reactor. 290 g of Triton.RTM. X100 at 25%, 900 g of
demineralized water and 3.2 g of ammonium sulphate solution at 10%
are added to the dispersion. The total content in Triton.RTM. X100
is equal to 17.7% with respect to the polymer, while the mixture
conductivity is equal to 810 .mu.S/cm, the pH equal to 8.3. The
homogeneous mixture is heated to 67.degree. C. under stirring.
[0159] At this point the same process described in the previous
step is repeated finally recovering a concentrated dispersion,
being coagula free, having a polymer content equal to 69.9% and a
Triton.RTM. X100 content equal to 2.1%. The PFOA content referred
to the polymer is 11 ppm.
[0160] The upper phase present in the reactor, rich in surfactant
Triton.RTM. X100, is treated as above to be reused in the
process.
[0161] Step e)
[0162] 700 g of the so obtained dispersion are introduced into a 3
l thermostatable reactor. 235 g of Triton.RTM. X100 at 25% by
weight, 900 g of demineralized water and 3.1 g of ammonium sulphate
solution at 10% are added to the dispersion. The total content in
Triton.RTM. X100 is equal to 15% with respect to the polymer, while
the mixture conductivity is equal to 790 .mu.S/cm, the pH 8.5. The
mixture, appearing homogeneous, is heated to 66.5.degree. C. under
stirring.
[0163] At this point the same process described in the previous
step is repeated finally recovering a concentrated dispersion,
being coagula free, having a polymer content equal to 69.9% and a
Triton.RTM. X100 content equal to 2.1%. The PFOA content referred
to the polymer is 3 ppm.
[0164] Step f)
[0165] 690 g of the so obtained dispersion are introduced into a 3
l thermostatable reactor. 240 g of Triton.RTM. X100 at 25%, 900 g
of demineralized water and 2.9 g of ammonium sulphate solution at
10% are added to the dispersion. The total content in Triton.RTM.
X100 is equal to 15.4% with respect to the polymer, while the
mixture conductivity is equal to 810 .mu.S/cm, the pH 8.4. The
mixture, appearing homogeneous, is heated to 66.5.degree. C. under
stirring.
[0166] At this point the same process described in the previous
step is repeated finally recovering a concentrated dispersion,
being coagula free, having a polymer content equal to 67.4% and a
Triton.RTM. X100 content equal to 2.3%. The PFOA content referred
to the polymer is <1 ppm.
[0167] Such dispersion has been formulated with a polymer content
equal to 60% by weight and a Triton.RTM. X100 equal to 3% by weight
with respect to the dispersion and it has been filtered on a 10
.mu.m Pall filter. The filter results free from polymer residues.
The stability to shear has been measured according to the above
method. It has been found that the dispersion stability is of 5 min
and 30 s, which represents a sufficiently high value to allow the
use thereof in the usual applications of the PTFE dispersions.
[0168] The dispersion is pumpable by using a common peristaltic
pump.
[0169] The specific conductivity of the concentrated dispersion
before the phase separation, the cloud point, the percentage by
weight of the polymer and of the nonionic surfactant and the PFOA
ppm in the concentrated phase obtained after heating at CP obtained
in steps a)- f) are summarized in Table 1.
Example 1-c
[0170] Purification and concentration of the latex using as
surfactant Genapol.RTM. X 080
[0171] Step a)
[0172] In a 3 litre thermostatable reactor 1,800 g of the PTFE
dispersion of the Example 1-a are introduced, having a solid
content equal to 30% and a PFOA content of 3,900 ppm with respect
to the polymer. As nonionic surfactant Genapol.RTM. X 080 having
CP=46.degree. C. is used. 360 g of the surfactant at 25% by weight
(16.7% by weight with respect to the polymer) and 9 g of ammonium
sulphate solution at 10% by weight (0.17% with respect to the
polymer) are added to the dispersion. The mixture, homogeneous, has
a specific conductivity at 250.degree. C. equal to 1,340 .mu.S/cm,
the pH is 4.6. The mixture is heated to 49.degree. C. under
stirring. When said temperature is reached, the stirring is stopped
and the mixture let decant for one hour at the same temperature. It
is observed separation of a concentrated phase in polymer in the
lower part of the reactor and of an upper phase rich in surfactant
Genapol.RTM. X 080, substantially not containing PTFE. At the end
the mixture is let cool at room temperature and from the lower part
of the reactor a concentrated dispersion is discharged, being
coagula free, having a polymer content of 70.5% by weight and a
Genapol.RTM. X 080 content equal to 2.2% by weight. The PFOA
content referred to the polymer is 640 ppm. The upper phase present
in the reactor, rich in surfactant Genapol.RTM. X 080, is treated
as indicated in the 1.sup.st step of Example 1-b to be reused in
the process.
[0173] Step b)
[0174] 750 g of the so obtained dispersion are introduced in a 3
litre thermostatable reactor. 260 g of Genapol.RTM. X 080 at 25% by
weight, 750 g of demineralized water and 4.5 g of ammonium sulphate
solution at 10% are added to the dispersion.
[0175] The total content in Genapol.RTM. X 080 is equal to 15.4%
with respect to the polymer, while the specific conductivity of the
mixture is 1,090 .mu.S/cm, the pH is 8.6. The homogeneous mixture
is heated to 48.degree. C. under stirring.
[0176] At this point the same process described in the previous
step is repeated finally recovering a concentrated dispersion,
being coagula free, having a polymer content equal to 68.8%, a
Genapol.RTM. X 080 content equal to 2.4% and a PFOA content
referred to the polymer of 160 ppm. The upper phase present in the
reactor, rich in surfactant Genapol.RTM. X 080, is treated as
mentioned above to be reused in the process.
[0177] Step c)
[0178] 755 g of the so obtained dispersion are introduced into a 3
l thermostatable reactor. 220 g of Genapol.RTM. X 080 at 25%, 1000
g of demineralized water and 4.5 g of ammonium sulphate solution at
10% are added to the dispersion. The total content in Genapol.RTM.
X 080 is equal to 14.1% with respect to the polymer, while the
specific conductivity of the mixture, homogeneous, is equal to 990
.mu.S/cm, the pH is 8.5. The mixture is heated to 48.degree. C.
under stirring.
[0179] At this point the same process described in the previous
step is repeated finally recovering a concentrated dispersion,
being coagula free, having a polymer content equal to 67.7% and a
Genapol.RTM. X 080 content equal to 2.2%. The PFOA content referred
to the polymer is 48 ppm. The upper phase present in the reactor,
rich in surfactant Genapol.RTM. X 080, is treated as above to be
reused in the process.
[0180] Step d)
[0181] 750 g of the so obtained dispersion are introduced into a 3
l thermostatable reactor. 300 g of Genapol.RTM. X 080 at 25%, 900 g
of demineralized water and 2.8 g of ammonium sulphate solution at
10% are added to the dispersion. The total content in Genapol.RTM.
X 080 is equal to 18% with respect to the polymer, while the
specific conductivity of the mixture is 880 .mu.S/cm, the pH is
8.5. The homogeneous mixture is heated to 48.degree. C. under
stirring.
[0182] At this point the same process described in the previous
step is repeated finally recovering a concentrated dispersion,
being coagula free, having a polymer content equal to 68%, a
Genapol.RTM. X 080 content equal to 2.3%. The PFOA content referred
to the polymer is 13 ppm.
[0183] The upper phase present in the reactor, rich in surfactant
Genapol.RTM. X 080, is treated as mentioned above to be reused in
the process.
[0184] Step e)
[0185] 735 g of the so obtained dispersion are introduced into a 3
l thermostatable reactor. 280 g of Genapol.RTM. X 080 at 25%, 900 g
of demineralized water and 2.9 g of ammonium sulphate solution at
10% are added to the dispersion. The total content in Genapol.RTM.
X 080 is equal to 17.4% with respect to the polymer, while the
specific conductivity of the mixture is equal to 840 .mu.S/cm, the
pH is 8.4. The mixture, which appears homogeneous, is heated to
47.degree. C. under stirring. At this point the same process
described in the previous step is repeated finally recovering a
concentrated dispersion, being coagula free, having a polymer
content equal to 68.50% and a Genapol.RTM. X 080 content equal to
2.3%. The PFOA content referred to the polymer is 4 ppm.
[0186] The dispersion has been formulated with a polymer content
equal to 60% by weight and a Genapol.RTM. X 080 content equal to 3%
by weight with respect to the dispersion and it has been filtered
on a 10 .mu.m Pall filter. The filter is polymer residue free. The
stability to shear has been measured according to the above method.
It has been found that the dispersion stability is of 5 min and 40
s, which represents a sufficiently high value to allow the use
thereof in the common applications of the PTFE dispersions.
[0187] The dispersion is pumpable using a common peristaltic
pump.
[0188] The specific conductivity of the concentrated dispersion
before the phase separation; the cloud point, the percentage by
weight of the polymer and of the nonionic surfactant and the PFOA
ppm in the concentrated phase obtained after heating at CP obtained
in steps a)-e) are summarized in Table 2.
Example 2 (Comparative)
[0189] Purification and Concentration of the Latex by Using as
Surfactant Triton.RTM. X100 but not Adding Salt
[0190] Step a)
[0191] In a 3 litre thermostatable reactor 1,800 g of the PTFE
dispersion of the Example 1-a are introduced, having a solid
content equal to 30% and a PFOA content equal to 3,900 ppm with
respect to the polymer. As nonionic surfactant, Triton.RTM. X100
having CP=67.degree. C. is used. 360 g of this surfactant at 25% by
weight (16.7% by weight with respect to the polymer) are added to
the dispersion. The mixture, homogeneous, has a specific
conductivity at 25.degree. C. equal to 370 .mu.S/cm, the pH is 4.7.
The mixture is heated to 76.degree. C. under stirring to have the
separation of the two phases. When this temperature is reached, the
stirring is stopped and the mixture let decant for one hour at the
same temperature. It is observed separation of a concentrated phase
in polymer in the lower part of the reactor and of an upper phase
rich in surfactant Triton.RTM. X100, substantially not containing
PTFE.
[0192] At the end the mixture is let cool to room temperature and
from the lower part of the reactor a concentrated dispersion is
discharged, being coagula free, having a polymer content of 67.7%
by weight and a Triton.RTM. X100 content equal to 1.7% by weight.
The PFOA content referred to the polymer is equal to 800 ppm. The
upper phase present in the reactor, rich in surfactant Triton.RTM.
X100, is treated with anionic exchange resins Amberjet.RTM.4400OH
(Rohm & Haas) for the PFOA removal and reused in the
process.
[0193] Step b)
[0194] 750 g of the so obtained dispersion are introduced into a 3
litre thermostatable reactor. 240 g of Triton.RTM. X100 at 25% by
weight, 750 g of demineralized water are added to the
dispersion.
[0195] The total content in Triton.RTM. X100 is equal to 14.3% with
respect to the polymer, while the specific conductivity of the
mixture is equal to 210 .mu.S/cm, the pH is 8.6. The homogeneous
mixture is heated to 70.degree. C. under stirring to have the phase
separation.
[0196] At this point the same process described in the previous
step is repeated finally recovering a concentrated dispersion,
being coagula free, having a polymer content equal to 62%, a
Triton.RTM. X100 content equal to 1.7% and a PFOA content referred
to the polymer equal to 315 ppm. The upper phase present in the
reactor, rich in surfactant Triton.RTM. X100, is treated as above
to be reused in the process.
[0197] Step c)
[0198] 800 g of the so obtained dispersion are introduced into a 3
l thermostatable reactor. 280 g of Triton.RTM. X100 at 25%, 1000 g
of demineralized water are added to the dispersion. The total
content in Triton.RTM. X100 is equal to 16.8% with respect to the
polymer, while the specific conductivity of the mixture,
homogeneous, is equal to 180 .mu.S/cm, the pH is 8.6. The mixture
is heated to 68.degree. C. under stirring.
[0199] At this point the same process described in the previous
step is repeated. At the end it is recovered with difficulty, owing
to the high viscosity, a concentrated dispersion having the
consistency of a gel, with a polymer content equal to 59% and a
Triton.RTM. X100 content equal to 2.6%.
[0200] The coagulum amount is not determinable under these
conditions.
[0201] The PFOA content with respect to the polymer is equal to 110
ppm.
[0202] The obtained dispersion is not pumpable and it is not
possible to carry out a further purification step to remove further
PFOA.
[0203] The specific conductivity of the concentrated dispersion
before the phase separation, the cloud point, the percentage by
weight of the polymer and of the nonionic surfactant and the PFOA
ppm in the concentrated phase oabtained after heating at CP
obtained in steps a)-c) are summarized in Table 3.
Example 3 (Comparative)
[0204] Purification and Concentration of the Latex by Using as
Surfactant Triton.RTM. X100 Under High Specific Conductivity
Conditions
[0205] Step a)
[0206] In a 3 litre thermostatable reactor 1800 g of the PTFE
dispersion of the Example 1-a are introduced, having a solid
content equal to 30% and a PFOA content equal to 3,900 ppm with
respect to the polymer. As nonionic surfactant, Triton.RTM. X100
having CP=67.degree. C. is used. 360 g of this surfactant at 25% by
weight (16.7% by weight with respect to the polymer) and 180 g of
ammonium sulphate solution at 10% by weight (3.3% with respect to
the polymer) are added to the dispersion. The mixture, homogeneous,
has a specific conductivity at 25.degree. C. equal to 9,800
.mu.S/cm, the pH is 4.4. The mixture is heated to 63.degree. C.
under stirring. When this temperature is reached, the stirring is
stopped and the mixture let decant for one hour at the same
temperature. It is observed separation of a concentrated phase in
polymer in the lower part of the reactor and of an upper phase rich
in surfactant Triton.RTM. X100, substantially not containing
PTFE.
[0207] At the end the mixture is let cool at room temperature and
from the lower part of the reactor a concentrated dispersion is
discharged, containing a coagulum amount of 0.15% with respect to
the polymer weight. The dispersion has a polymer content of 67% by
weight and a Triton.RTM. X100 content equal to 2.4% by weight. The
PFOA content referred to the polymer is equal to 740 ppm. The upper
phase present in the reactor, rich in surfactant Triton.RTM. X100,
is treated with anionic exchange resins Amberjet.RTM.4400OH (Rohm
& Haas) for the PFOA removal and reused in the process.
[0208] Step b)
[0209] 780 g of the so obtained dispersion are introduced into a 3
litre thermostatable reactor. 230 g of Triton.RTM. X100 at 25% by
weight, 750 g of demineralized water and 140 g of ammonium sulphate
solution at 10% are added to the dispersion.
[0210] The total content in Triton.RTM. X100 is equal to 14.6% with
respect to the polymer, while the specific conductivity of the
mixture is equal to 9,600 .mu.S/cm, the pH is 8.3. The homogeneous
mixture is heated to 63.degree. C. under stirring.
[0211] At this point the same process described in the previous
step is repeated finally recovering a concentrated dispersion,
containing a coagulum amount of 2% by weight on the polymer. The
dispersion has a polymer content equal to 62%, a Triton.RTM. X100
content equal to 2.7% and a PFOA content referred to the polymer of
210 ppm. The upper phase present in the reactor, rich in surfactant
Triton.RTM. X100, is treated as above to be reused in the
process.
[0212] Step c)
[0213] 700 g of the so obtained dispersion are introduced into a 3
l thermostatable reactor. 230 g of Triton.RTM. X100 at 25%, 1,000 g
of demineralized water and 130 g of ammonium sulphate solution at
10% are added to the dispersion. The total content in Triton.RTM.
X100 is equal to 17.5% with respect to the polymer, while the
specific conductivity of the mixture, homogeneous, is equal to
9,300 .mu.S/cm, the pH is 8.3. The mixture is heated to 63.degree.
C. under stirring.
[0214] At this point the same process described in the previous
step is repeated, finally recovering a concentrated dispersion,
containing a coagulum amount equal to 8% by weight on the polymer.
The dispersion has a polymer content equal to 61% and a Triton.RTM.
X100 content equal to 2.1%. The PFOA content with respect to the
polymer is equal to 80 ppm.
[0215] Such dispersion has been formulated with a polymer content
equal to 60% by weight and a Triton.RTM. X100 content equal to 3%
by weight with respect to the dispersion and it has been filtered
on a 10 .mu.m Pall filter. On the filter a remarkable amount of
polymer residues is present. The stability to shear has been
measured according to the above method. It has been found that the
dispersion stability is of 2 min and 10 s, which represents a quite
insufficient value to allow the use thereof in the usual
applications of the PTFE dispersions.
[0216] The dispersion, after separation from the coagulum, is
pumpable using a normal peristaltic pump.
[0217] The specific conductivity of the concentrated dispersion
before the phase separation, the cloud point, the percentage by
weight of the polymer and of the nonionic surfactant and the PFOA
ppm in the concentrated phase oabtained after heating at CP in
steps a)-c) are summarized in Table 4.
1TABLE 1 Results obtained in steps a)-f) of the Example 1-b. Steps
a) b) c) d) e) f) Dispersion before the phase separation Specific
Conductivity 1280 1010 950 810 790 810 (.mu.S/cm) Cloud Point
(.degree. C.) 68 67.5 67.5 67 66.5 66.5 Lower concentrated phase
after the phase separation Polymer weight % 69 71.5 67 69,9 69.9
67.4 Nonionic surfactant 2 2 2.1 2.1 2.1 2.3 weight % PFOA ppm on
the 620 150 42 11 3 <1 polymer Coagulum (% w/w) <0.005
<0.005 <0.005 <0.005 <0.005 <0.005
[0218]
2TABLE 2 Results obtained in steps) a)-e) of the Example 1-c. Steps
a) b) c) d) e) Dispersion before the phase separation Specific 1340
1090 990 880 840 Conductivity (.mu.S/cm) Cloud Point (.degree. C.)
49 48 48 48 47 Lower concentrated phase after the phase separation
Polymer weight % 70.5 68.8 67.7 68 68.5 Nonionic surfactant 2.2 2.4
2.2 2.3 2.3 weight % PFOA ppm on the 640 160 48 13 4 polymer
Coagulum (% w/w) <0.005 <0.005 <0.005 <0.005
<0.005
[0219]
3TABLE 3 Results obtained in steps a)-c) of the Example 2
(comparative) Steps a) b) c) Dispersion before the phase separation
Specific Conductivity 370 210 110 (.mu.S/cm) Cloud Point (.degree.
C.) 76 70 68 Lower concentrated phase after the phase separation
Polymer weight % 67.7 62 59 Nonionic surfactant 1.7 1.7 2.6 weight
% PFOA ppm on the 800 315 110 polymer Coagulum (% w/w) <0.005
<0.005 n.d.
[0220]
4TABLE 4 Results obtained in steps a)-c) of the Example 3
(comparative) Steps a) b) c) Dispersion before the phase separation
Specific Conductivity 9,800 9,600 9,300 (.mu.S/cm) Cloud Point
(.degree. C.) 63 63 63 Lower concentrated phase after the phase
separation Polymer weight % 67 62 61 Nonionic surfactant 2.4 2.7
2.1 weight % PFOA ppm on the 740 210 80 polymer Coagulum (% w/w)
0.15 2 8
* * * * *